Degree Type

Thesis

Date of Award

2010

Degree Name

Master of Science

Department

Chemistry

First Advisor

Victor S. Lin

Abstract

Enzymatic and thermochemical catalysis are both important industrial processes. However, the thermal requirements for each process often render them mutually exclusive: thermochemical catalysis requires high temperature that denatures enzymes. One of the long-term goals of this project is to design a thermocatalytic system that could be used with enzymatic systems in situ to catalyze reaction sequences in one pot; this system would be useful for numerous applications e.g. conversion of biomass to biofuel and other commodity products. The desired thermocatalytic system would need to supply enough thermal energy to catalyze thermochemical reactions, while keeping the enzymes from high temperature denaturation. Magnetic nanoparticles are known to generate heat in an oscillating magnetic field through mechanisms including hysteresis and relaxational losses. We envisioned using these magnetic nanoparticles as the local heat source embedded in sub–micron size mesoporous support to spatially separate the particles from the enzymes. In this study, we set out to find the magnetic materials and instrumental conditions that are sufficient for this purpose.

Magnetite was chosen as the first model magnetic material in this study because of its high magnetization values, synthetic control over particle size, shape, functionalization and proven biocompatibility. Our experimental designs were guided by a series of theoretical calculations, which provided clues to the effects of particle size, size distribution, magnetic field, frequency and reaction medium. Materials of theoretically optimal size were synthesized, functionalized, and their effects in the oscillating magnetic field were subsequently investigated. Under our conditions, the materials that clustered e.g. silica–coated and PNIPAM–coated iron oxides exhibited the highest heat generation, while iron oxides embedded in MSNs and mesoporous iron oxides exhibited the least bulk heating. It is worth noting that the specific loss power of PNIPAM–coated Fe3O4 was peculiarly high, and the heat loss mechanism of this material remains to be elucidated.

Since thermocatalysis is a long-term goal of this project, we also investigated the effects of the oscillating magnetic field system for the synthesis of 7–hydroxycoumarin–3–carboxylic acid. Application of an oscillating magnetic field in the presence of magnetic particles with high thermal response was found to effectively increase the reaction rate of the uncatalyzed synthesis of the coumarin derivative compared to the room temperature control.

DOI

https://doi.org/10.31274/etd-180810-195

Copyright Owner

Chorthip Peeraphatdit

Language

en

Date Available

2012-04-30

File Format

application/pdf

File Size

53 pages

Included in

Chemistry Commons

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